Process of performing organic chemical reactions with alkali metal compounds



Patented Mar. 24, 1942 2.277.359 paoosss or raaroamo ORGANIC CHEM- ICAL,REACTIONS WITH ALKALI COMPOUNDS DIETAL Erik Schirm, Dessau, Anhalt,Richard Hueter, Dessau-Bosslau, Anhalt, and Heinz-Joachim Engelbrecht,Dessau, Anhalt, Germany, assignors, by mesne assignments, to PatchemA.-G. zur Beteiligung an Patenten und Sonstigen Erfindungsrechten aui'Chemlsche Verfahren," Zurich, Switzerland, a co p ration of SwitzerlandNo Drawing. Application December 16, 1938, Se-

rial No. 246,070. In Germany December 18,

11 Claims.

We known that by the catalytic high-pressure hydrogenation of furfurolwe obtain as principal alcoholic reaction productstetra-hydro-furfurylalcohol, 12- and 1,5-pentandiol and small portionsof low mono-valent alcohols.

Now, as a result of extended researches, it has been found that in thepresence of these hydrogenation-products a great number of chemicalconversions can advantageously be performed. It is a fact that in spiteof the numerous solvents available for the performing oforganic-chemical reactions we hithertohave not had a suitable mediumcombining a comparatively low volatility with a high dissolving power,particularly when the reactions involved alkali metal and alkali metalcompounds. In such reactions we usually usedmethanol, ethanol, butanolor the like as solvents, but these agents proved too volatile.lnperforming chemical conversions in their presence we generally wereforced to, use an autoclave, i. e., we had to choose a way which is notadvantageous. On the other hand, the alcoholic hydrogenation-products offurfurol, which have at least equal, and in most cases,

even better dissolving power than the foregoing alcohols, have such lowvolatility that chemical conversions can be performed in their'presencein an open vessel at temperatures up to 240 C. This means anextraordinary simplification in many commercial processes.

Compared with cyclohexanol and its homologues, which have a higherboiling-point and .also are frequently used to assist the abovementionedconversions, the hydrogenation-products of furfurol show a surprisinglyhigh dissolving power for alkali metal compounds very often used forsuch reactions such as alkali metal hydroxides, alkali metalhalogenides, alkali metal sulfides, alkali metal polysulfides, alkalimetal sulfohydrates, alkali metal rhodanides, alkali metal enolates,alkali metal alcoholates, alkali metal .phenolates, alkali metalnaphtholates, etc., and also for high molecular organic compounds. Thusthese higher molecular compounds can be converted with theaforementioned alkali metal compounds in a particularly smooth reactionpreviously not attainable, and also in a very satisfactory yield. Themiscibility of the hydrogenation-products of furfurol with waterfacilitates in many cases the extraction of the reaction products aswell as the sepa- Y ration of the reaction products from water-..soluble media and by-products. This property constituted an additionalelement oi'superiority over the aforesaid well-known solvents.

' mercial significance.

Among these conversions, the numerous conversions of the alkali metalsulfides, -polysulfldes and -sulfohydrates with organic compoundscontaining replaceable halogen-atoms, or nitrogroups, and with thewell-known initial compounds used for the production of sulfur dyes foruse in dyeing operations are all of great com- Conversions of this kindcan be performed according to the present method under much'morefavourable conditions and with higher outputs of purer products thanhitherto possible with any other 'known method.

Other solvents and diluents, in addition to the hydrogenation-productsof furfurolconsidered herein, may be jointly employed, such as low fattyalcohols, cycloheiganol, methyl-cyclohexanol, chlorohydrocarbons,di-oxane, benzolhydrocarbons, phenols and the like.

Example 1 Forty-four parts by weight of sodium-hydroxide are dissolved,while warming, in 500 parts by weight of the rawfurfurol-hydrogenation-product, having a boiling point varying betweenand 240 C. Then 48 parts by weight or spermaceti are added whereupon themixture is heated for 2 hours up to C. Now first the solvent and thenthe cetyl-alcohol are distilled off under greatly reduced pressure.There remains as a residue sodium palmitate which forms a clear solutionin hot water. Both-of the split-products of the spermaceti are producedin the theoretical yields.

Example 2 One hundred forty-eight and five-tenths parts by weight ofn-octyl chloride, 183 of finely pulwith cold water and then subjected toa careful fractional distillation under reduced pressure. The yield ofthe thus resulting n-octyl-iodide is very satisfactory. q

7 Example 3V r h 7 One hundred and fifty-six parts by weight oicommercial sodium sulfide (with 60% of Na s) are dissolved, whilewarming in 800 parts by weight of tetra-hydroiurfuryl-alcoho1. Thelsourated at 50 to 55 C. with carbon-dioxide,

whereupon 289 parts byv weight oi octadecylchloride areadded andfthenthe'mass is heated at 60-65" C. ford hours while stirring. Now

800 parts by weight of warm water are added, the aqueous layer drawn oiland the oil washed with hot water until. the alkaline reaction ceases.Then the wateri'n the reaction mass is distilled on under reducedpressure. Two hundred and thirty-five parts by weightoi'octadecylmercaptan. which equals 82% of the theoretical yield areobtained.

Example 4 one hundred and firty-eig'ht' artsjb Weight ofp-chloro-nitrobenzol are dissolved, while slightly warming, in 250 partsby weight of tetrahydro-furfuryl-alcohol. Then a warm solution of 98parts by weight of commercial sodium sulby filtering, and

cohol are gradually added. Now', the reactionmixture is stirred for 2hoursjat 90 to- 95 ll,

.diluted with 1000 parts by weight of water; cooled, and then theprecipitate is filtered ofi. As

Forty-one parts by weight of n-dodecyl chloride, 23 of potassiumrhodanide and 200 of a fraction of the hydrogenation-product fromthefurturol-hydrogenation, separated from its low boil'- f ing fraction andboiling between 150 and 2l0 0.,

are stirred atl50 to 160 C. until the separation cipitatedsodium-chloride the solution is distilled Example 7v 7 Three hundredandfifty parts by weight of commercial sodium sulfide (with 60% of NazS)and 345 weight parts of sulfur are dissolved in 3000 parts byweight oftetrahydro-iuriuryl-alcohol. lution, ireed or iron-sulfide by?filtering, is sat- Then 276 parts by weight of p-phenylamino-p'-hydroxy-diphenylamine are added and the mixture so stirrediorZ i hoursat 100 C. Now the 'diluent' is distilled off under reduced pressure andthe residue dissolved in water. After filtering, the blue dye-stuff isprecipitated from the solution by blowing air into it.

Example 8 To a solution of 11.5 parts by weight of metallic sodiumin 250parts by'weight of tetrahydroi urfuryl alcohol, 40 parts by weight ormalonic ester are added at approximately 8 C. Immediately thereafter 160parts by weight of octa- '25 iide (with 60% of Na s) freed fromiron-sulfide V v 24 parts by weight oi'sulfur in .750 parts.by weight oftetrahydro iuriuryl-aldecyl-chloride and 1.6 parts by weight ofpotassinus-iodide are added. The reaction-mixture is heated-whilestirring, to 100 C. andretained thereat'until the solution is neutral.After separating on the precipitated sodium chloride and afterdistilling oil the tetrahydrofurfuryl-alcohol the 'alkylated'malonicester is saponified; the potassium-salt is'converted intotlieicalcium-salt and the latteris thenpurified by extraction with etherand alcohol; By acidulating we obtain the free acid which,after-purifyingby fractional crystallization from methanol shows a"melting point of 86 to 87 ejam an acid-number of of sodium-chloride iscompleted. The reactionmixture, cooled down a little, then liberatedfrom subjected to fractional distillation in .vacuo. Duringthisoperation-the solvent-passes over first and then then-dodecyl-rhodanideis obtained in a very remarkable yield. r

Example 6 Two hundred and sixty parts by weight of 7 commercialsodium-sulfide -(with 60% of NazS) are dissolved in 3000 parts byweightof warm tetrahydro-furfuryl alcohol. After filtering ofi the ironsulfide, 706 parts by weightof m-nitrobenzaldehyde dioctadecylmercaptol(produced according to the U. S. A. patent application Ser. No. 205,989)are stirred into this solution within half an hour at 60 to 659C. Thenthe stirring 3 is continued ior'2 hours at 80 to 85? C., where-' upon itis cooled down to 15 C. and the'separation-product quickly separamd bysuction filtrasodium-chloride by filtering and the filtrate is' IExample 9 A solution of 11.5 parts byweight of metallic sodium in 250parts by weight oi'tetrahydrofurfuryl-alcohol is'warmed' with 70 partsby weight of benzyl-chloride fupfto 40-50". C., until the solution isneutral. 'Aiter' separating the prefuriuryl-alcohol 8.5"parts by weightof p-nitrophenol, are stirred i by weight of ectadeeyl--.cl:doride areslowly added at 100 C. Then 1.8 parts at approximately 14:0 ,C.andfinally 0.18 part by weightg of potassium-iodide 'are added,whereupon'stirring is continued until asample shows a neutral reaction.After cooling the, crystal- I lized 'octadecyl-p-nitrcphenol-ether: isseparated tion andpressed. The residue-is freed from the .unseparatedsalts and the colouring impurities by repeated washings with hot waterand then dried. The yield ofm-amino-benzaldehyde-dioctadecyl-mercaptol,- a grey-yellowish powdergrowing nearly colourless after re-crystallizing [frommethyl-'cyclohexane and having a flashpoint of to 66 0., is are partsbyweight and equals 90% of the theoretical'yield.

from tetrahydro-iurfurylalcohol by suction filtration, then washedwithvwater tojget, it free from sodium-chloride and finally dried. Thereaction product is obtained in a quantity which equals 93% or thetheoretical yield-and has a melting point of 70 to 71 C.

We claim:

, l. In a process for producing an organic reaction product of an alkalimetalc ompound difficultysoluble organic solvents and an organiccompound, the improvement which comprises dissolving the alkali. metalcompound man-alcoholic hydrogenation product or iuriurol and carryingout the reaction of said alkali metal compound with, said organiccompound in the presence of said alcoholic hydrogenation product as asolvent for the reagents.

2. In the production of organic reaction products involving reacting analkali metal compound with an organic compound, the improvement whichcomprises dissolving the reagents in the alcoholic hydrogenationproducts of furfurol and performing the reaction in the presence of saidalcoholic hydrogenation products in an open vessel at temperatures lessthan 240 C.

3. In the production of organic reaction products involving reacting anorganic compound with an alkali metal compound selected from the groupconsisting V of alkali metals, alkali metal hydroxides, alkali metalsulfides, alkali metal polysulfides and alkali metal hydrosulfides, theimprovement which comprises performing the reaction in the presence ofan alcoholic hydrogenation product of furfurol.

4. In the reaction of an organic halide with an alkali metal compound,the improvement which comprises performing the reaction in the presenceof an alcoholic hydrogenation product of furfurol.

5. In the reaction of an organic nitro-compound with an alkali metalcompound, the improvement which comprises performing the reaction in thepresence of an alcoholic hydrogenation product of furfurol.

6. In the production of sulfur dyes involving the reaction of a sulfuralkali metal compound with an organic nitrogen compound which producessulfur dyes upon reaction with said alkali metal compound, theimprovement which comprises performing the reaction in the presence ofan alcoholic hydrogenation product of furfurol.

7, In the reaction of an aliphatic halide with an alkali metal compound,the improvement which comprises reacting said compound in the presenceof an alcoholic hydrogenation product of furfurol.

8. In a process for producing an organic reaction product of aninorganic alkali metal compound with an organic compound, theimprovement which comprises dissolving said inorganic alkali metalcompound in tetrahydrofurfurol alcohol and carrying out the reaction ofsaid alkali metal compound with said organic compound in the presence ofsaid tertahydrofurfurol alcohol as the solvent.

9. In a process for producing an organic reaction product, theimprovement which comprises reacting an organic halide with'an alkalimetal compound in the presence of pentandiol as the solvent.

10. In a process for producing an organic reaction product of an alkalimetal sulfide with an organic compound, the improvement which comprisescarrying out the reaction in the presence of tetrahydrofurfurol alcoholas the solvent.

11. In the process of producing an organic reaction product of an alkalimetal compound difficultly soluble in organic solvents, the improvementwhich comprises reacting said alkali metal compound with a reactiveorganic compound in the presence of an alcoholic hydrogenation productof furfurol as a dissolving agent.

ERIK SCHIRM.

RICHARD HUETER. HEINZ-JOACHIM ENGELBRECHT.

